Catalytic Ketonization over Oxide Catalysts (Part XIV): The Ketonization and Cross-Ketonization of Anhydrides, Substituted Acids and Esters
A series of 20 wt.% MO<sub>2</sub>/S catalysts (where M = Ce, Mn or Zr and S = SiO<sub>2</sub> or Al<sub>2</sub>O<sub>3</sub>) were prepared using various precursors of the active phases. The resulting catalysts were characterized using different metho...
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MDPI AG
2024-01-01
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| author | Marek Gliński Małgorzata Gidzińska Łukasz Czerwiński Kasper Drozdowski Ewa M. Iwanek (nee Wilczkowska) Andrzej Ostrowski Dariusz Łomot |
| author_facet | Marek Gliński Małgorzata Gidzińska Łukasz Czerwiński Kasper Drozdowski Ewa M. Iwanek (nee Wilczkowska) Andrzej Ostrowski Dariusz Łomot |
| author_sort | Marek Gliński |
| collection | DOAJ |
| description | A series of 20 wt.% MO<sub>2</sub>/S catalysts (where M = Ce, Mn or Zr and S = SiO<sub>2</sub> or Al<sub>2</sub>O<sub>3</sub>) were prepared using various precursors of the active phases. The resulting catalysts were characterized using different methods (XRD, TPR and S<sub>BET</sub>). For the first time, anhydrides were used as potential starting materials for ketone synthesis. This novel reaction was performed on various aliphatic anhydrides in the presence of catalysts within a temperature range of 523–723 K. For all anhydrides, except for pivalic anhydride, the appropriate ketones were obtained with good or very good yields. The vapor-phase catalytic ketonization of esters of benzene-1,x-dicarboxylic acids (x = 2, 3 or 4) with acetic acid were studied in the range of 673–723 K in order to obtain 1,x-diacetylbenzenes. Their yields strongly increased with an increase in the x value (0, 8 and 43% for x = 2, 3 and 4, respectively). The presence of acetophenone as a side product was always noted. In the case of ω-phenylalkanoic acids, their vapor-phase ketonization with acetic acid led to the formation of appropriate ketones with 47–49% yields. Much lower yields of ketones (3–19%) were obtained for acids and ethyl esters containing heterocycle substituents (with O or S atoms) and/or vinyl groups. In the reaction between ethyl 4-nitrophenylacetate and acetic acid, only the products of ester decomposition (<i>p</i>-toluidine and <i>p</i>-nitrotoluene) were determined. |
| first_indexed | 2024-03-08T03:53:10Z |
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| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-08T03:53:10Z |
| publishDate | 2024-01-01 |
| publisher | MDPI AG |
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| series | Molecules |
| spelling | doaj.art-e7cdcba633fb47aba268b92d35dae5912024-02-09T15:18:42ZengMDPI AGMolecules1420-30492024-01-0129358410.3390/molecules29030584Catalytic Ketonization over Oxide Catalysts (Part XIV): The Ketonization and Cross-Ketonization of Anhydrides, Substituted Acids and EstersMarek Gliński0Małgorzata Gidzińska1Łukasz Czerwiński2Kasper Drozdowski3Ewa M. Iwanek (nee Wilczkowska)4Andrzej Ostrowski5Dariusz Łomot6Faculty of Chemistry, Warsaw University of Technology, Noakowskiego 3, 00-662 Warsaw, PolandFaculty of Chemistry, Warsaw University of Technology, Noakowskiego 3, 00-662 Warsaw, PolandFaculty of Chemistry, Warsaw University of Technology, Noakowskiego 3, 00-662 Warsaw, PolandFaculty of Chemistry, Warsaw University of Technology, Noakowskiego 3, 00-662 Warsaw, PolandFaculty of Chemistry, Warsaw University of Technology, Noakowskiego 3, 00-662 Warsaw, PolandFaculty of Chemistry, Warsaw University of Technology, Noakowskiego 3, 00-662 Warsaw, PolandInstitute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw, PolandA series of 20 wt.% MO<sub>2</sub>/S catalysts (where M = Ce, Mn or Zr and S = SiO<sub>2</sub> or Al<sub>2</sub>O<sub>3</sub>) were prepared using various precursors of the active phases. The resulting catalysts were characterized using different methods (XRD, TPR and S<sub>BET</sub>). For the first time, anhydrides were used as potential starting materials for ketone synthesis. This novel reaction was performed on various aliphatic anhydrides in the presence of catalysts within a temperature range of 523–723 K. For all anhydrides, except for pivalic anhydride, the appropriate ketones were obtained with good or very good yields. The vapor-phase catalytic ketonization of esters of benzene-1,x-dicarboxylic acids (x = 2, 3 or 4) with acetic acid were studied in the range of 673–723 K in order to obtain 1,x-diacetylbenzenes. Their yields strongly increased with an increase in the x value (0, 8 and 43% for x = 2, 3 and 4, respectively). The presence of acetophenone as a side product was always noted. In the case of ω-phenylalkanoic acids, their vapor-phase ketonization with acetic acid led to the formation of appropriate ketones with 47–49% yields. Much lower yields of ketones (3–19%) were obtained for acids and ethyl esters containing heterocycle substituents (with O or S atoms) and/or vinyl groups. In the reaction between ethyl 4-nitrophenylacetate and acetic acid, only the products of ester decomposition (<i>p</i>-toluidine and <i>p</i>-nitrotoluene) were determined.https://www.mdpi.com/1420-3049/29/3/584ketonizationanhydridescarboxylic acidsestersketonesmetal oxide catalysts |
| spellingShingle | Marek Gliński Małgorzata Gidzińska Łukasz Czerwiński Kasper Drozdowski Ewa M. Iwanek (nee Wilczkowska) Andrzej Ostrowski Dariusz Łomot Catalytic Ketonization over Oxide Catalysts (Part XIV): The Ketonization and Cross-Ketonization of Anhydrides, Substituted Acids and Esters Molecules ketonization anhydrides carboxylic acids esters ketones metal oxide catalysts |
| title | Catalytic Ketonization over Oxide Catalysts (Part XIV): The Ketonization and Cross-Ketonization of Anhydrides, Substituted Acids and Esters |
| title_full | Catalytic Ketonization over Oxide Catalysts (Part XIV): The Ketonization and Cross-Ketonization of Anhydrides, Substituted Acids and Esters |
| title_fullStr | Catalytic Ketonization over Oxide Catalysts (Part XIV): The Ketonization and Cross-Ketonization of Anhydrides, Substituted Acids and Esters |
| title_full_unstemmed | Catalytic Ketonization over Oxide Catalysts (Part XIV): The Ketonization and Cross-Ketonization of Anhydrides, Substituted Acids and Esters |
| title_short | Catalytic Ketonization over Oxide Catalysts (Part XIV): The Ketonization and Cross-Ketonization of Anhydrides, Substituted Acids and Esters |
| title_sort | catalytic ketonization over oxide catalysts part xiv the ketonization and cross ketonization of anhydrides substituted acids and esters |
| topic | ketonization anhydrides carboxylic acids esters ketones metal oxide catalysts |
| url | https://www.mdpi.com/1420-3049/29/3/584 |
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